JP2816618B2 - Method for removing bischloromethyl ether contained in pivalic acid chloromethyl ester - Google Patents
Method for removing bischloromethyl ether contained in pivalic acid chloromethyl esterInfo
- Publication number
- JP2816618B2 JP2816618B2 JP31547791A JP31547791A JP2816618B2 JP 2816618 B2 JP2816618 B2 JP 2816618B2 JP 31547791 A JP31547791 A JP 31547791A JP 31547791 A JP31547791 A JP 31547791A JP 2816618 B2 JP2816618 B2 JP 2816618B2
- Authority
- JP
- Japan
- Prior art keywords
- bischloromethyl ether
- pom
- pivalic acid
- chloromethyl ester
- acid chloromethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は（ＣＨ3)3 ＣＣＯ2 ＣＨ
2 Ｃｌで示されるピバリン酸クロロメチルエステル（以
下ＰＯＭと略称する）をピバロイルクロライドとパラホ
ルムアルデヒド（以下ＰＦＡと略称する）との反応によ
り製造する際に副生する著しく毒性の強い現在製造禁止
物質に指定されている構造式（ＣｌＣＨ2)2 Ｏで示され
るビスクロロメチルエ−テル（以下ＢＣＭと略称する）
を工業的に製造されたＰＯＭより有利に完全に除去する
方法に関するものである。ＰＯＭ又はその誘導体は医
薬、農薬を始め、多くの有機合成化合物の原料又は中間
体として有用な化合物である。それだけに副生成物とし
て生成する有害なＢＣＭの除去は工業的に著しく重要な
意味がある。The present invention relates to (CH 3 ) 3 CCO 2 CH
The production ban, which is a byproduct of the production of pivalic acid chloromethyl ester represented by 2 Cl (hereinafter abbreviated as POM) by the reaction of pivaloyl chloride and paraformaldehyde (hereinafter abbreviated as PFA), which is extremely toxic. Bischloromethyl ether represented by the structural formula (ClCH 2 ) 2 O designated as a substance (hereinafter abbreviated as BCM)
In a more advantageous manner than POM produced industrially. POM or a derivative thereof is a compound useful as a raw material or an intermediate of many organic synthetic compounds including pharmaceuticals and agricultural chemicals. Therefore, the removal of harmful BCM generated as a by-product has significant industrial significance.
【０００２】[0002]
【従来の技術】従来ピバロイルクロライドとＰＦＡを原
料としてＺｎＣｌ2 などのルイス酸を触媒としてＰＯＭ
を製造する方法は公知である。〔特開昭48−14646 ，
Ｊ，Ａ，Ｃ，Ｓ，89，5439(1967)〕 その反応式は下記の通りである。 （ＣＨ3)3 ＣＣＯ2 ＣＨ2 Ｃｌ ………… (1) またこの反応式(1) に於ては次の副反応が生ずる。 〔Descude,M.,Bull,Soc,chim.(3),27,867(1902) 〕 ２（ＣＨ3 )3ＣＣＯ2 ＣＨ2 Ｃｌ───→ 〔（ＣＨ3)3 ＣＣＯ〕2 Ｏ＋（ＣｌＣＨ2)2 Ｏ ………… (2) 反応式(2) によつて副生するＢＣＭは前記したように著
しく毒性が強いため製造禁止物質に指定されている化合
物である。2. Description of the Related Art Conventionally, POM is produced using pivaloyl chloride and PFA as raw materials and a Lewis acid such as ZnCl 2 as a catalyst.
The method for producing is well known. [JP-A-48-14646,
J, A, C, S, 89, 5439 (1967)] The reaction formula is as follows. (CH 3 ) 3 CCO 2 CH 2 Cl (1) In the reaction formula (1), the following side reaction occurs. [Descude, M., Bull, Soc, chim. (3), 27,867 (1902)] 2 (CH 3 ) 3 CCO 2 CH 2 Cl─── → [(CH 3 ) 3 CCO] 2 O + (ClCH 2 ) 2 O ... (2) BCM produced as a by-product according to the reaction formula (2) is a compound which is specified as a production banned substance because it is extremely toxic as described above.
【０００３】前記の方法では反応式(2) より明らかなよ
うにＢＣＭの副生は避けられない。水洗方法又は蒸留方
法によつてＢＣＭを削減することはできても、それら従
来の方法によつてはＢＣＭを完全に除去することは不可
能である。In the above-mentioned method, as is apparent from the reaction formula (2), by-product of BCM cannot be avoided. Although BCM can be reduced by a washing method or a distillation method, it is impossible to completely remove BCM by these conventional methods.
【０００４】[0004]
【発明が解決しようとする課題】上記に鑑み本発明者等
はピバロイルクロライドとＰＦＡとの反応によるＰＯＭ
の製造において副生するＢＣＭを完全に除去するために
鋭意研究した結果、製造されたＰＯＭの水洗時にアンモ
ニア又はアミン類などのＮＨ2 基を有する化合物又はア
ルコ−ル類を添加することによつて、反応系より副生物
として生成するＢＣＭを完全に除去可能なことを見出し
た。この本発明者等の知見に基づいて本発明は、上記反
応式(1) において、副生する反応式(2) に示すＢＣＭを
完全に除去することを目的とするものである。SUMMARY OF THE INVENTION In view of the above, the present inventors have developed POM by the reaction of pivaloyl chloride with PFA.
As a result of intensive studies to completely remove the BCM produced as a by-product in the production of POM, it has been found that when the produced POM is washed with water, a compound having an NH 2 group such as ammonia or amines or an alcohol is added. Discovered that BCM generated as a by-product from the reaction system could be completely removed. An object of the present invention based on the findings of the present inventors is to completely remove the BCM represented by the reaction formula (2) by-produced in the reaction formula (1).
【０００５】[0005]
【課題を解決するための手段】本発明は（ＣＨ3)3 ＣＣ
Ｏ2 ＣＨ2 Ｃｌで示されるピバリン酸クロロメチルエス
テル製造時に副生物として生成する（ＣｌＣＨ2)2 Ｏで
示されるビスクロロメチルエ−テルに反応する物質とし
てアンモニア又はアミン類などのＮＨ2 基を有する化合
物又はアルコ−ル類を添加して反応系から（ＣｌＣＨ2)
2 Ｏを除去する方法に関し、更に副生するビスクロロメ
チルエ−テルと反応する化合物が少なくとも一種類であ
ることを特徴とする方法を提供するものである。The present invention provides (CH 3 ) 3 CC
NH 2 groups such as ammonia and amines are used as a substance which reacts with bischloromethyl ether represented by (ClCH 2 ) 2 O which is produced as a by-product during production of pivalic acid chloromethyl ester represented by O 2 CH 2 Cl (ClCH 2 ) from the reaction system by adding a compound or alcohols having
Another object of the present invention is to provide a method for removing 2 O, wherein at least one compound reacts with bischloromethyl ether as a by-product.
【０００６】本発明は本発明者等の見出したＰＯＭの製
造法に従つて、ピバロイルクロライドとＰＦＡの反応に
溶媒を使用することなしに、触媒としてＺｎＣｌ2 等の
ルイス酸を使用し、助触媒として塩化チオニルを使用し
てＰＯＭを生成せしめ、しかる後反応液に水及びアンモ
ニア又はＮＨ2 基を有する化合物又はアルコ−ル類を添
加し、洗浄を行い、乾燥剤で脱水後減圧蒸留してＰＯＭ
が製造される。According to the present invention, the present invention provides a method for producing POM using a Lewis acid such as ZnCl 2 as a catalyst without using a solvent in the reaction between pivaloyl chloride and PFA, POM was produced using thionyl chloride as a co-catalyst, then water and ammonia or a compound having an NH 2 group or alcohols were added to the reaction solution, washed, dehydrated with a desiccant and distilled under reduced pressure. POM
Is manufactured.
【０００７】本発明に使用されるＮＨ2 基を有する化合
物としてはメチルアミン、エチルアミン、プロピルアミ
ン、イソプロピルアミン、ブチルアミンのような低級脂
肪族第１アミン類又は尿素、アンモニア類、好適にはメ
チルアミン、エチルアミン、アンモニア、尿素等であ
る。更にアルコ−ル類としてはメタノ−ル、エタノ−
ル、プロピルアルコ−ル、イソプロピロアルコ−ル、ブ
チルアルコ−ル等の低級脂肪族アルコ−ルのほかに、ア
リルアルコ−ルのような脂肪族不飽和アルコ−ル、シク
ロペンタノ−ルのような脂環式アルコ−ルが使用される
が、好適にはメタノ−ル、エタノ−ル、イソプロパノ−
ル等である。アンモニア又はＮＨ2 基を含有する化合物
はピバロイルクロライドに対して５〜100 モル％の範囲
で使用される。アルコ−ル類の使用量はピバロイルクロ
ライドに対して10〜25モル％の範囲が好適である。洗浄
温度はＰＯＭを分解させず、ＢＣＭを分解させるために
は30〜50℃の範囲が好適である。また同時に使用される
洗浄水の量は、制限はないが洗浄効果よりしてピバロイ
ルクロライドに対して50〜100 重量％の範囲が好適であ
る。洗浄時間は２〜３時間を必要とする。The compound having an NH 2 group used in the present invention includes lower aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine and butylamine, or urea and ammonia, preferably methylamine. , Ethylamine, ammonia, urea and the like. Further, alcohols include methanol and ethanol.
Alicyclic alcohols such as allyl alcohol, aliphatic unsaturated alcohols such as allyl alcohol, and cycloaliphatic alcohols such as cyclopentanol, in addition to lower aliphatic alcohols such as alcohol, propyl alcohol, isopropyl alcohol and butyl alcohol. Formula alcohols are used, preferably methanol, ethanol, isopropanol.
And so on. Compounds containing ammonia or NH 2 groups is used in the range of 5 to 100 mol% relative to pivaloyl chloride. The use amount of alcohols is preferably in the range of 10 to 25 mol% based on pivaloyl chloride. The washing temperature is preferably in the range of 30 to 50 ° C. in order to decompose BOM without decomposing POM. The amount of washing water used at the same time is not limited, but is preferably in the range of 50 to 100% by weight based on pivaloyl chloride due to the washing effect. The washing time requires 2-3 hours.
【０００８】[0008]
【実施例１】 本発明者等の見出したＰＯＭの製造方法
に従つて純度98.0％のピバロイルクロライド246.0gと塩
化チオニル47.6g 及び塩化亜鉛4.0gを仕込み、60℃まで
昇温後、撹拌しながら純度95％のＰＦＡ75.9g を５時間
かけて添加した後、60℃で５時間反応せしめた。反応終
了後室温まで冷却し、25％アンモニア水115.0g及び水7
5.0g を添加し、40℃で２時間洗浄を行つた。その後分
液して下層の水層を抜き出し、ＣａＣｌ2 30g を添加し
て脱水し、濾過してＣａＣｌ2 を除去後蒸留して、無色
透明の液体であるＰＯＭ、266.5g（収率88.3％、純度9
9.8％）を得た。このＰＯＭ中のＢＣＭをガスクロマト
グラフイ−で測定した結果、検出されなかつた。Example 1 246.0 g of pivaloyl chloride having a purity of 98.0%, 47.6 g of thionyl chloride, and 4.0 g of zinc chloride were charged in accordance with the method of producing POM found by the present inventors, heated to 60 ° C., and stirred. While adding 55.9 g of PFA having a purity of 95% over 5 hours, the mixture was reacted at 60 ° C. for 5 hours. After the reaction is completed, cool to room temperature, 115.0 g of 25% aqueous ammonia and water 7
5.0 g was added and washed at 40 ° C. for 2 hours. Thereafter, liquid separation was carried out, and the lower aqueous layer was withdrawn, 30 g of CaCl 2 was added to dehydrate the mixture, filtration was performed to remove CaCl 2, and distillation was carried out to obtain 266.5 g of a colorless and transparent liquid POM (yield: 88.3%, Purity 9
9.8%). The BCM in this POM was not detected as a result of measurement by gas chromatography.
【０００９】[0009]
【実施例２】 純度95％のＰＦＡ8.70g と塩化亜鉛0.5g
と反応溶媒としてＣＨ2 Ｃｌ2 10.0g を仕込み、10℃ま
で冷却後撹拌しながら、純度98％のピバロイルクロライ
ド30.75gと塩化チオニル4.45g の混合溶液を２時間で滴
下した後、10℃で８時間反応した。反応後、水20.0g と
メタノ−ル2.0gを添加し、40℃で２時間洗浄を行つた
後、分液して粗ＰＯＭ40.4g （収率94.8％、純度88.4
％）を得た。このＰＯＭ中のＢＣＭをガスクロマトグラ
フイ−で測定した結果、検出されなかつた。[Example 2] 8.70 g of 95% pure PFA and 0.5 g of zinc chloride
And 10.0 g of CH 2 Cl 2 as a reaction solvent. After cooling to 10 ° C. and stirring, a mixed solution of 30.75 g of pivaloyl chloride having a purity of 98% and 4.45 g of thionyl chloride was added dropwise over 2 hours. For 8 hours. After the reaction, 20.0 g of water and 2.0 g of methanol were added, washed at 40 ° C. for 2 hours, and separated to separate 40.4 g of crude POM (yield 94.8%, purity 88.4%).
%). The BCM in this POM was not detected as a result of measurement by gas chromatography.
【００１０】[0010]
【実施例３】 純度98.0％のピバロイルクロライド24.6
g と塩化チオニル4.76g 及び塩化亜鉛0.4gを仕込み、60
℃まで昇温後撹拌しながら純度95％のＰＦＡ7.59g を１
時間かけて添加した後、60℃で４時間反応せしめた。反
応終了後、室温まで冷却し、水16.0g 及び尿素7.2gを仕
込み、40℃で２時間洗浄を行つた。その後分液して粗Ｐ
ＯＭ25.1g （収率83.2％、純度99.8％）を得た。このＰ
ＯＭ中のＢＣＭをガスクロマトグラフイ−で測定した結
果、検出されなかつた。Example 3 Pivaloyl chloride having a purity of 98.0% 24.6
g, 4.76 g of thionyl chloride and 0.4 g of zinc chloride.
After raising the temperature to 100 ° C, add 7.59 g of 95% pure PFA while stirring.
After the addition over time, the mixture was reacted at 60 ° C. for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, charged with 16.0 g of water and 7.2 g of urea, and washed at 40 ° C. for 2 hours. After that, liquid separation
25.1 g of OM (83.2% yield, 99.8% purity) was obtained. This P
BCM in OM was not detected as a result of measurement by gas chromatography.
【００１２】[0012]
【発明の効果】本発明の方法で製造されたＰＯＭは有毒
性の大なるＢＣＭを含有せず、従つて本発明は高純度の
ＰＯＭを安全、かつ高収率で得ることができ、本発明の
工業的価値は著しく大きい。According to the present invention, the POM produced by the method of the present invention does not contain toxic BCM, and therefore, the present invention can provide high-purity POM in a safe and high yield. Has a remarkably large industrial value.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｃ 43/12 Ｃ０７Ｃ 43/12 (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 69/63 C07C 67/14 C07C 67/60 C07C 67/62 C07C 43/12 C07C 41/46──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 identification code FI C07C 43/12 C07C 43/12 (58) Fields investigated (Int.Cl. 6 , DB name) C07C 69/63 C07C 67/14 C07C 67/60 C07C 67/62 C07C 43/12 C07C 41/46
Claims (2)
示されるピバリン酸クロロメチルエステルの製造時に、
副生物として生成する構造式（ＣｌＣＨ2)2Ｏで示され
るビスクロロメチルエ−テルの除去にビスクロロメチル
エ−テルと反応する化合物として、アンモニア、ＮＨ2
基を有する化合物又はアルコ−ル類を添加することを特
徴とするピバリン酸クロロメチルエステルに含有するビ
スクロロメチルエ−テルの除去法。1. A method for producing pivalic acid chloromethyl ester represented by the structural formula (CH 3 ) 3 CCO 2 CH 2 Cl,
As a compound that reacts with bischloromethyl ether to remove bischloromethyl ether represented by the structural formula (ClCH 2 ) 2 O generated as a by-product, ammonia, NH 2
A method for removing bischloromethyl ether contained in chloromethyl pivalate, comprising adding a compound having a group or alcohols.
合物が少なくとも１種類である請求項１記載のピバリン
酸クロロメチルエステルに含有するビスクロロメチルエ
−テルの除去法。2. The method for removing bischloromethyl ether contained in pivalic acid chloromethyl ester according to claim 1, wherein at least one compound reacts with bischloromethyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31547791A JP2816618B2 (en) | 1991-11-01 | 1991-11-01 | Method for removing bischloromethyl ether contained in pivalic acid chloromethyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31547791A JP2816618B2 (en) | 1991-11-01 | 1991-11-01 | Method for removing bischloromethyl ether contained in pivalic acid chloromethyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05125020A JPH05125020A (en) | 1993-05-21 |
| JP2816618B2 true JP2816618B2 (en) | 1998-10-27 |
Family
ID=18065832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31547791A Expired - Fee Related JP2816618B2 (en) | 1991-11-01 | 1991-11-01 | Method for removing bischloromethyl ether contained in pivalic acid chloromethyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2816618B2 (en) |
-
1991
- 1991-11-01 JP JP31547791A patent/JP2816618B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05125020A (en) | 1993-05-21 |
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